TWI911270B - Cleaning method for substrate - Google Patents

Abstract

This invention provides a substrate cleaning method in one embodiment, which inhibits copper corrosion without significantly impairing the removability (peelability) of the resin mask and without significantly increasing the residue on the cleaned substrate. This invention relates to a substrate cleaning method comprising the following steps: using a cleaning agent composition containing component A, component B, and component C to peel the resin mask from a substrate having a copper metal layer and a resin mask on its surface. Component A: Quaternary ammonium hydroxide represented by formula (I) and an amine represented by formula (II) Component B: Reducing agent Component C: Water

Description

Cleaning method for substrate

This invention relates to a cleaning agent composition for resin mask peeling, a cleaning method for substrates using the same, and a method for manufacturing electronic components.

In recent years, personal computers and various electronic devices have been developing towards lower power consumption, higher processing speeds, and miniaturization. The wiring of the packaging substrates and other components in these devices is becoming increasingly finer each year. To date, the formation of such fine wiring and connection terminals such as posts or bumps has mainly used the metal masking method. However, due to its low versatility and difficulty in meeting the miniaturization requirements of wiring, there is a shift towards other innovative methods.

As a novel method, it is known to use a dry film anti-corrosion agent as a thick film resin mask to replace a metal mask. This resin mask is eventually peeled off and removed. Regarding the cleaning agents used for peeling and removal, it is known to use cleaning agents containing an alkali and water for peeling resin masks. For example, in Japanese Patent Application Publication No. 2019-112498 (Patent Document 1), in order to provide a resin mask peeling and cleaning method with excellent resin mask removal and continuous operation stability, the following resin mask peeling and cleaning method is disclosed, which uses a cleaning agent composition containing a specific quaternary ammonium hydroxide, a specific amine, and water.

Furthermore, technologies to inhibit corrosion of metal films after cleaning are also being developed. For example, Japanese Patent Application Publication No. 2007-256955 (Patent Document 2) discloses a chemical cleaning composition for cleaning with an anti-corrosion stripping solution that provides excellent cleaning effect and does not corrode metal films after cleaning. The composition contains an anti-corrosion agent selected from the group consisting of organic amine compounds, organic solvents, triazole corrosion inhibitors, hydroxyphenols, alkyl gallic acid esters, and reducing agents, and water.

In one embodiment, this invention relates to a method for cleaning a substrate, comprising the following steps: using a cleaning agent composition containing component A, component B, and component C, to peel off the resin mask from a substrate having a copper-containing metal layer and a resin mask on its surface. Component A: Quaternary ammonium hydroxide represented by formula (I) and an amine represented by formula (II) Component B: Reducing agent Component C: Water [Chemical 1] In formula (I) above, ^R1 , ^R2 , ^R3 and ^R4 are each independently selected from at least one of methyl, ethyl, propyl, hydroxymethyl, hydroxyethyl and hydroxypropyl. [Chemical 2] In formula (II) above, ^R5 represents at least one of hydrogen atom, methyl, ethyl and aminoethyl, ^R6 represents at least one of hydrogen atom, hydroxyethyl, hydroxypropyl, methyl and ethyl, and ^R7 represents at least one of aminoethyl, hydroxyethyl and hydroxypropyl.

In one embodiment, the present invention relates to a method for manufacturing an electronic component, comprising the following steps: using the cleaning method of the present invention to peel off the resin mask from a substrate having a copper metal layer and a resin mask on its surface.

This invention relates to a detergent composition for resin masking removal, comprising the following components A, B, and C. Component A: a quaternary ammonium hydroxide represented by formula (I) and an amine represented by formula (II); Component B: a reducing agent; Component C: water. [Chemical 3] In formula (I) above, ^R1 , ^R2 , ^R3 and ^R4 are each independently selected from at least one of methyl, ethyl, propyl, hydroxymethyl, hydroxyethyl and hydroxypropyl. [Chemical 4] In formula (II) above, ^R5 represents at least one of hydrogen atom, methyl, ethyl and aminoethyl, ^R6 represents at least one of hydrogen atom, hydroxyethyl, hydroxypropyl, methyl and ethyl, and ^R7 represents at least one of aminoethyl, hydroxyethyl and hydroxypropyl.

This invention relates to the use of a cleaning agent composition for resin mask stripping, which is used as a cleaning agent in the manufacture of electronic components. The cleaning agent composition for resin mask stripping contains the following components A, B, and C. Component A: Quaternary ammonium hydroxide represented by formula (I) and an amine represented by formula (II). Component B: Reducing agent. Component C: Water. [Chemical 5] In formula (I) above, ^R1 , ^R2 , ^R3 and ^R4 are each independently selected from at least one of methyl, ethyl, propyl, hydroxymethyl, hydroxyethyl and hydroxypropyl. [Chemical 6] In formula (II) above, ^R5 represents at least one of hydrogen atom, methyl, ethyl and aminoethyl, ^R6 represents at least one of hydrogen atom, hydroxyethyl, hydroxypropyl, methyl and ethyl, and ^R7 represents at least one of aminoethyl, hydroxyethyl and hydroxypropyl.

Regarding the formation of fine wiring on printed circuit boards, etc., high detergency is required for the detergent composition in order to reduce resin mask residue and the residue of additives contained in solder or plating solutions used in the formation of fine wiring or bumps. Here, resin mask refers to that formed using an anti-corrosion agent whose physical properties, such as solubility in developer, change due to light or electron beams. Based on the reaction method with light or electron beams, anti-corrosion agents can be broadly classified into negative and positive types. Negative resists have the property of reduced solubility in developer upon exposure. After exposure and development, the exposed areas of a layer containing negative resist (hereinafter referred to as a "negative resist layer") are used as a resin mask. Positive resists have the property of increased solubility in developer upon exposure. After exposure and development, the exposed areas of a layer containing positive resist (hereinafter referred to as a "positive resist layer") are removed, and the unexposed areas are used as a resin mask. By using resin masks with these properties, fine connections in circuit boards, such as metal wiring, metal pillars, or solder bumps, can be formed.

However, with the miniaturization of wiring, it becomes increasingly difficult to remove resin masks present in the fine gaps, requiring detergent compositions with high resin mask removal properties. Furthermore, since corrosion of copper used in most wiring or connectors reduces the quality and value of the packaging substrate, detergent compositions require high corrosion resistance. In addition, residues on the substrate after cleaning can hinder subsequent etching processes, thus requiring detergent compositions that can reduce these residues.

Therefore, the present invention provides a method for cleaning a substrate that inhibits copper corrosion without significantly impairing the removability (peelability) of the resin mask and without significantly increasing the residue on the cleaned substrate. It also provides a method for manufacturing electronic components and a cleaning agent composition for resin mask peeling.

This invention is based on the view that by using a specific organic nitrogen-containing compound (component A) in combination with a reducing agent (component B), it is possible to inhibit copper corrosion and efficiently remove resin mask from the substrate surface. In addition, it is possible to reduce the residue on the substrate after cleaning.

This invention relates to a method for cleaning a substrate (hereinafter also referred to as "the cleaning method of this invention"), comprising the following steps: using a cleaning agent composition containing component A, component B, and component C, to peel off the resin mask from a substrate having a copper metal layer and a resin mask on its surface. Component A: Quaternary ammonium hydroxide represented by formula (I) above and an amine represented by formula (II) above Component B: Reducing agent Component C: Water

According to the present invention, a cleaning method is provided that can inhibit copper corrosion without significantly impairing the removability (peelability) of the resin mask and without significantly increasing the residue on the substrate after cleaning. Furthermore, by using the cleaning method of the present invention, high-quality electronic components can be obtained with higher yield. Moreover, by using the cleaning method of the present invention, electronic components with fine wiring patterns can be manufactured efficiently.

While some details of the mechanism of action of this invention remain unclear, the following conjectures are made: In this invention, it is believed that a specific organic nitrogen-containing compound (component A) penetrates into the resin mask, promoting the dissociation of the alkali-soluble resin incorporated into the resin mask. This dissociation, in turn, causes a repulsion of the charges generated, thereby promoting the peeling of the resin mask. Furthermore, it is believed that the specific organic nitrogen-containing compound (component A) also participates in the etching (corrosion) of copper. However, it is believed that in this invention, by using a specific organic nitrogen-containing compound (component A) and a reducing agent (component B), the reducing agent (component B) suppresses the positive charge on the copper surface, thereby inhibiting copper etching (corrosion) caused by the coordination of the specific organic nitrogen-containing compound (component A). It is believed that, as a result, copper etching (corrosion) is suppressed in the presence of the specific organic nitrogen-containing compound (component A), and good peeling performance (resin mask removal) is exhibited. Furthermore, it is believed that because the reducing agent (component B) is non-coating rather than coating-type, it can suppress copper etching (corrosion) and reduce residues on the substrate after cleaning. However, this invention may also be interpreted in a way that is not limited to this mechanism.

In this invention, the peeled-off or removed resin mask refers to a mask used to protect the surface of a material from the effects of etching, plating, heating, etc., i.e., a mask that functions as a protective film. Examples of resin masks in one or more embodiments include: an anti-corrosion layer after exposure and development steps, an anti-corrosion layer subjected to at least one of exposure and development processes (hereinafter also referred to as "exposed and/or developed"), or a hardened anti-corrosion layer. Examples of resin materials forming the resin mask in one or more embodiments include: a film-like photosensitive resin, an anti-corrosion film, or a photoresist. A general-purpose anti-corrosion film can be used. Resin masking, in one or more embodiments, is used as a mask for copper or tin plating processes.

[Detergent Composition] The detergent composition of the present invention, in one or more embodiments, is a resin masking and peeling detergent composition comprising components A, B, and C, described below.

[Organic Nitrogen Compound (Component A)] The detergent composition of this invention comprises a combination of two components: a quaternary ammonium hydroxide represented by formula (I) (Component A1) and an amine represented by formula (II) (Component A2) (hereinafter also referred to as "Component A"). Component A1 may be one or a combination of two or more. Component A2 may be one or a combination of two or more.

[Chemistry 7]

In the above formula (I), ^R1 , ^R2 , ^R3 and ^R4 are each independently selected from at least one of methyl, ethyl, propyl, hydroxymethyl, hydroxyethyl and hydroxypropyl.

[Chemistry 8]

In formula (II) above, ^R5 represents at least one of hydrogen atom, methyl, ethyl and aminoethyl, ^R6 represents at least one of hydrogen atom, hydroxyethyl, hydroxypropyl, methyl and ethyl, and ^R7 represents at least one of aminoethyl, hydroxyethyl and hydroxypropyl.

As a quaternary ammonium hydroxide (component A1) represented by formula (I), examples include salts containing quaternary ammonium cations and hydroxides. Specific examples of quaternary ammonium hydroxides include tetramethyl ammonium hydroxide (TMAH), tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, 2-hydroxyethyltrimethyl ammonium hydroxide (choline), 2-hydroxyethyltriethyl ammonium hydroxide, 2-hydroxyethyltripropyl ammonium hydroxide, 2-hydroxypropyltrimethyl ammonium hydroxide, 2-hydroxypropyltriethyl ammonium hydroxide, 2-hydroxypropyltriethyl ammonium hydroxide, and 2-hydroxypropyltripropyl ammonium hydroxide. The resin comprises at least one of the following: dimethyl bis(2-hydroxyethyl)ammonium hydroxide, diethyl bis(2-hydroxyethyl)ammonium hydroxide, dipropyl bis(2-hydroxyethyl)ammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, tris(2-hydroxyethyl)ethylammonium hydroxide, tris(2-hydroxyethyl)propylammonium hydroxide, tetra(2-hydroxyethyl)ammonium hydroxide, and tetra(2-hydroxypropyl)ammonium hydroxide. Among these, tetramethylammonium hydroxide and tetraethylammonium hydroxide are preferred from the viewpoint of improving the masking removeability of the resin, and tetramethylammonium hydroxide (TMAH) is more preferred.

Examples of amines represented by formula (II) (component A2) include alkanolamines, primary to tertiary amines, and heterocyclic compounds. Specific examples of amines include monoethanolamine (MEA), monoisopropanolamine, N-methylmonoethanolamine, N-methylisopropanolamine, N-ethylmonoethanolamine, N-ethylisopropanolamine, diethanolamine, diisopropanolamine, N-dimethylmonoethanolamine, N-dimethylmonoisopropanolamine, N-methyldiethanolamine, N-methyldiisopropanolamine, N-methyldiisopropanolamine, N-diethylmonoethanolamine, N-diethylmonoisopropanol ... At least one of the following: propanolamine, N-ethyldiethanolamine, N-ethyldiisopropanolamine, N-(β-aminoethyl)ethanolamine, N-(β-aminoethyl)isopropanolamine, N-(β-aminoethyl)diethanolamine, N-(β-aminoethyl)diisopropanolamine, 1-methylpiperazine, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)piperazine, ethylenediamine, and diethylenetriamine. Among these, monoethanolamine (MEA) and diethanolamine are preferred from the viewpoint of improving resin mask removal properties, and monoethanolamine (MEA) is more preferred.

Regarding the content of component A (the total content of component A1 and component A2) when using the detergent composition of the present invention, from the viewpoint of not significantly impairing the resin mask removal (peelability) and not significantly increasing the residue on the substrate after cleaning, thereby inhibiting copper corrosion, it is preferably 5% by mass or more, more preferably 6% by mass or more, and even more preferably 7% by mass or more. Furthermore, from the same viewpoint, it is preferably 15% by mass or less, more preferably 13% by mass or less, and even more preferably 12% by mass or less. More specifically, when using the detergent composition of the present invention, the content of component A is preferably 5% by mass to 15% by mass, more preferably 6% by mass to 13% by mass, and even more preferably 7% by mass to 12% by mass. When component A1 is a combination of two or more components, the content of component A1 refers to the total content of those components. When component A2 is a combination of two or more components, the content of component A2 refers to the total content of those components.

Regarding the ratio (mass ratio A1/A2) of component A1 to component A2 in the detergent composition of the present invention, from the viewpoint of not significantly impairing the resin mask removal (peelability) and not significantly increasing the residue on the substrate after cleaning, thereby inhibiting copper corrosion, it is preferably 0.1 or more, more preferably 0.3 or more, and even more preferably 0.6 or more. Furthermore, from the same viewpoint, it is preferably 2 or less, more preferably 1.5 or less, and even more preferably 1 or less. More specifically, the mass ratio A1/A2 is preferably 0.1 or more and 2 or less, more preferably 0.3 or more and 1.5 or less, and even more preferably 0.6 or more and 1 or less.

In this invention, "the content of each component when the detergent composition is used" refers to the content of each component at the time of washing, that is, the point at which the detergent composition is first used for washing.

[Reducing Agent (Component B)] The detergent composition of the present invention contains a reducing agent (hereinafter also referred to as "Component B"). Component B, from the viewpoint of inhibiting copper corrosion by not significantly impairing the resin mask removal (peelability) and not significantly increasing the residue on the substrate after cleaning, can be selected from at least one of ascorbic acid (hereinafter also referred to as "Component B1") and an N-oxide compound containing a nitrogen-containing heteroaromatic ring in which at least one hydrogen atom of the nitrogen-containing heteroaromatic ring is replaced by a hydroxyl group (hereinafter also referred to as "Component B2"). Among these, Component B2 is preferred from the viewpoint of the stability of the detergent composition. Examples of the aforementioned salts include: alkaline metal salts, alkaline earth metal salts, organic amine salts, and ammonium salts. Component B may be used alone or in combination with two or more other components.

As component B1, examples include one or more of L-ascorbic acid, D-ascorbic acid, isoascorbic acid, and their salts. The nitrogen-containing heterocyclic skeleton of component B2 contains at least one nitrogen atom forming an N-oxide. The nitrogen-containing heterocyclic ring contained in component B2, in one or more embodiments, may be a monocyclic or bicyclic condensed ring. From the viewpoint of inhibiting copper corrosion by not significantly impairing the resin mask removal (peelability) and not significantly increasing the residue on the cleaned substrate, the number of nitrogen atoms in the nitrogen-containing heteroaromatic ring included in component B2 is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. The nitrogen-containing heteroaromatic ring skeleton included in component B2 may, in one or more embodiments, be a pyridine-N-oxide skeleton. In this invention, the pyridine-N-oxide skeleton represents a structure in which the nitrogen atoms contained in the pyridine ring form N-oxides. Component B2 may be selected from at least one N-oxide compound having at least one hydrogen atom substituted with a hydroxyl group in a pyridine ring, and at least one of such salts. Specific examples of component B2 include 2-hydroxypyridine-N-oxide, etc.

In this invention, N-oxide compounds represent compounds having N-oxide groups (N→O groups) in one or more embodiments. N-oxide compounds may have one or more N→O groups, and from the viewpoint of ease of acquisition, the number of N→O groups is preferably one.

From the perspective of inhibiting copper corrosion by not significantly impairing the resin mask removal (peelability) and not significantly increasing the residue on the substrate after washing, component B is preferably at least one of ascorbic acid and 2-hydroxypyridine-N-oxide.

Regarding the content of component B in the cleaning agent composition of the present invention, from the viewpoint of not significantly impairing the resin mask removal (peelability) and not significantly increasing the residue on the substrate after cleaning, thereby inhibiting copper corrosion, it is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more. Furthermore, from the same viewpoint, it is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less. More specifically, the content of component B is preferably 0.05% by mass or more and 5% by mass, more preferably 0.1% by mass or more and 3% by mass, and even more preferably 0.2% by mass or more and 1% by mass or less. When component B is a combination of two or more, the content of component B refers to the total content of those components.

Regarding the ratio (mass ratio A/B) of component A to component B in the detergent composition of the present invention, from the viewpoint of not significantly impairing the resin mask removal (peelability) and not significantly increasing the residue on the substrate after cleaning, thereby inhibiting copper corrosion, it is preferably 8 or more, more preferably 14 or more, further preferably 18 or more, further preferably 20 or more, and from the same viewpoint, preferably 50 or less, more preferably 45 or less, further preferably 40 or less. More specifically, the mass ratio A/B is preferably 8 or more and 50 or less, more preferably 14 or more and 45 or less, further preferably 18 or more and 45 or less, further preferably 20 or more and 40 or less.

[Water (Component C)] The water (hereinafter also referred to as "Component C") contained in the detergent composition of this invention may, in one or more embodiments, be ion-exchanged water, reverse osmosis water, distilled water, pure water, and ultrapure water, etc.

The content of component C in the detergent composition of the present invention can be set to the residue after removing components A, component B and any of the components described below. Specifically, regarding the content of component C in the cleaning agent composition of the present invention, from the perspectives of not significantly impairing the resin mask removal (peelability), not significantly increasing the residue on the substrate after cleaning and thus inhibiting copper corrosion, reducing the drainage treatment load, and reducing the impact on the substrate, it is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, further preferably 80% by mass or more, and from the same perspective, preferably 99% by mass or less, more preferably 98% by mass or less, further preferably 97% by mass or less. More specifically, when the detergent composition of the present invention is used, the content of component C is preferably 50% by mass or more and 99% by mass, more preferably 60% by mass or more and 99% by mass, further preferably 70% by mass or more and 98% by mass, and even more preferably 80% by mass or more and 97% by mass.

Regarding the use of the detergent composition of the present invention, the total amount of components A, B and C is preferably 60% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, from the viewpoint that it does not significantly impair the resin mask removal (peelability) and does not significantly increase the residue on the substrate after cleaning, thereby inhibiting copper corrosion.

[Organic Solvent (Component D)] From the viewpoint that the cleaning agent composition of the present invention, in one or more embodiments, does not significantly impair the resin mask removal (peelability) and does not significantly increase the residue on the cleaned substrate, thereby inhibiting copper corrosion, it may further contain an organic solvent (hereinafter also referred to as "Component D"). Component D may be one type or a combination of two or more types. As Component D, in one or more embodiments, examples include at least one solvent selected from glycol ethers and aromatic ketones. As a glycol ether, from the same viewpoint, examples include compounds having a structure obtained by adding 1 to 3 moles of ethylene glycol to an alcohol having 1 to 8 carbon atoms. Specific examples of glycol ethers include at least one of diethylene glycol monobutyl ether (BDG), ethylene glycol monobenzyl ether, diethylene glycol monohexyl ether, ethylene glycol monophenyl ether, and diethylene glycol diethyl ether. From the same perspective, examples of aromatic ketones include acetophenone, etc.

When the detergent composition of the present invention contains component D, the content of component D during use of the detergent composition of the present invention, from the viewpoint of not significantly impairing the resin mask removal (peelability) and not significantly increasing the residue on the substrate after cleaning, thereby inhibiting copper corrosion, is preferably 1% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2% by mass or more. Furthermore, from the same viewpoint, it is preferably 40% by mass or less, more preferably 20% by mass or less, and even more preferably 5% by mass or less. More specifically, the content of component D during use is preferably 1% by mass or more and 40% by mass or less, more preferably 1.5% by mass or more and 20% by mass or less, and even more preferably 2% by mass or more and 5% by mass or less. When component D is a combination of two or more, the content of component D refers to the total content of those components.

[Chlorinating Agent (Component E)] The detergent composition of the present invention, in one or more embodiments, may further contain a chelating agent (hereinafter also referred to as "Component E") from the viewpoint that it does not significantly impair the resin mask removal (peelability) and does not significantly increase the residue on the substrate after cleaning, thereby inhibiting copper corrosion. Component E may be one type or a combination of two or more types. As Component E, for example, a compound having at least one acid group selected from carboxyl and phosphonic acid groups can be cited. From the same viewpoint, a preferred compound is one having preferably four or fewer of the aforementioned acid groups. Specific examples of component E, in one or more embodiments, include: aminotrimethylenephosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, and etidronic acid (1-hydroxyethane-1,1-diphosphonic acid, HEDP). Among these, from the viewpoint of reducing environmental impact, compounds that do not contain nitrogen atoms, such as 2-phosphonobutane-1,2,4-tricarboxylic acid and etidronic acid (HEDP), are preferred.

When the detergent composition of the present invention contains component E, the content of component E during use of the detergent composition of the present invention, from the viewpoint of not significantly impairing the resin mask removal (peelability) and not significantly increasing the residue on the substrate after cleaning, thereby inhibiting copper corrosion, is preferably 0.5% by mass or more, more preferably 1% by mass or more, and from the same viewpoint, preferably 5% by mass or less, more preferably 3% by mass or less. More specifically, the content of component E during use is preferably 0.5% by mass or more and 5% by mass or less, more preferably 1% by mass or more and 3% by mass or less. When component E is a combination of two or more, the content of component E refers to the total content of those components.

[Component F: Ammonium Salt of Organic Acid] From the viewpoint that the cleaning agent composition of the present invention, in one or more embodiments, does not significantly impair the resin mask removal (peelability) and does not significantly increase the residue on the substrate after cleaning, thereby inhibiting copper corrosion, it may further contain at least one ammonium salt of organic acid (hereinafter also referred to as "Component F"). From the same viewpoint, the ammonium salt of organic acid is preferably an ammonium salt of a carboxylic acid having 1 to 5 carbon atoms, and more preferably ammonium formate. Component F may be one type or a combination of two or more types.

When the detergent composition of the present invention contains ingredient F, the content of ingredient F when using the detergent composition of the present invention is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more, and from the same point of view, preferably 2% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1% by mass or less. More specifically, the content of component F is preferably 0.1% by mass or more and 2% by mass, more preferably 0.2% by mass or more and 1.5% by mass, and even more preferably 0.3% by mass or more and 1% by mass. When component F is a combination of two or more, the content of component F refers to the total content of them.

In one or more embodiments of the present invention, the detergent composition preferably further comprises ingredients D, E and F, from the viewpoint of improving the removal of resin masks.

[Other Ingredients] Without impairing the effectiveness of the invention, the detergent composition of this invention may contain other ingredients besides those listed above (A to F), as needed. Examples of such other ingredients include those commonly used in detergents, such as: alkalis other than ingredient A, organic solvents other than ingredient D, surfactants, chelating agents other than ingredient E, thickeners, dispersants, rust inhibitors, polymers, co-solvents, antioxidants, preservatives, defoamers, and antibacterial agents. When the detergent composition of the present invention is used, the content of other components is preferably 0% to 2% by mass, more preferably 0% to 1.5% by mass, further preferably 0% to 1.3% by mass, and even more preferably 0% to 1% by mass.

In one or more embodiments, the detergent composition of the present invention is preferably free of triazole preservatives. For example, in one or more embodiments, the content of triazole preservatives in the detergent composition of the present invention during use is less than 0.005% by mass.

When the detergent composition of the present invention is used, the total content of organic matter from components A, B and any components (components D, E, F, and other components) is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, and even more preferably 16% by mass or less, from the viewpoint of reducing the drainage treatment load and reducing the impact on the substrate. Furthermore, from the viewpoint of improving the resin mask removal performance, it is preferably 2% by mass or more, more preferably 3% by mass or more, even more preferably 4% by mass or more, and even more preferably 6% by mass or more. More specifically, when the detergent composition of the present invention is used, the total content of organic matter from ingredients A, B, C and any ingredients (ingredients D, E, F, and other ingredients) is preferably 2% by mass or more and 30% by mass, more preferably 3% by mass or more and 25% by mass, even more preferably 4% by mass or more and 20% by mass, and even more preferably 6% by mass or more and 16% by mass.

[Method for Manufacturing a Detergent Composition] The detergent composition of the present invention can be manufactured by blending component A, component B, component C, and any other component (component D, component E, component F, or other components) as needed, using known methods. For example, in one or more embodiments, the detergent composition of the present invention may be formulated by blending at least component A, component B, and component C. Therefore, the present invention relates to a method for manufacturing a detergent composition, which includes the step of blending at least component A, component B, and component C. In the present invention, "blending" includes mixing component A, component B, component C, and any other component (component D, component E, component F, or other components) simultaneously or in any order. In the manufacturing method of the detergent composition of the present invention, the preferred formulation of each component can be set to be the same as the preferred content of each component in the detergent composition of the present invention described above.

The detergent composition of this invention can be in a form suitable for direct cleaning, or it can be prepared as a concentrate with a reduced amount of water (component C) within a range that will not cause separation or precipitation and thus compromise storage stability. From the viewpoint of transportation and storage, the detergent composition is preferably prepared as a concentrate with a dilution ratio of 3 times or more, and from the viewpoint of storage stability, it is preferably prepared as a concentrate with a dilution ratio of 30 times or less. The detergent concentrate can be diluted with water (component C) to achieve the aforementioned concentration (i.e., the concentration at the time of washing) of each component (component A, component B, component C, component D, component E, component F, and other components) before use. Alternatively, the detergent concentrate can be used by adding each component separately at the time of use. In this invention, "at the time of use" or "at the time of washing" for the concentrated detergent concentrate refers to the state in which the detergent concentrate has been diluted.

[Object to be Cleaned] In one or more embodiments, the object to be cleaned is a substrate having a copper-containing metal layer and a resin mask on its surface. Examples of such substrates include insulator plates or films. Therefore, the cleaning agent composition of the present invention, in one or more embodiments, can be used to clean substrates having a copper-containing metal layer and a resin mask on their surface. In one or more embodiments, the copper-containing metal layer is a copper-plated layer. The copper-plated layer can be formed, for example, by an electroless copper plating process. In one or more embodiments, the copper-containing metal layer is used as metal wiring. A substrate having a copper-containing metal layer and a resin mask on its surface has undergone at least one of the following processes in one or more embodiments: soldering with a resin mask and plating. In one or more embodiments, the substrate has a copper-containing metal layer or a tin-containing metal layer with a thickness of 15 μm or more. From the viewpoint of electrical characteristics and manufacturability, the thickness of the copper-containing metal layer or the tin-containing metal layer with a thickness of 15 μm or more is preferably 15 μm or more and 85 μm or less, more preferably 20 μm or more and 80 μm or less, and even more preferably 30 μm or more and 70 μm or less. A copper-containing or tin-containing metal layer with a thickness of 15 μm or more is used in one or more embodiments as metal wiring or wiring connections.

In one or more embodiments, the object to be cleaned is an object coated with a resin mask. Therefore, the detergent composition of the present invention can be used in one or more embodiments to clean objects coated with a resin mask. As an object coated with a resin mask, in one or more embodiments, examples include electronic components with copper-containing metal portions and resin masks on their surfaces, and intermediate manufacturing processes thereof. Examples of electronic components include at least one component selected from printed circuit boards, wafers, and metal plates such as copper and aluminum plates. The aforementioned intermediate manufacturing processes are intermediate products in the manufacturing steps of electronic components, including intermediate products after resin mask treatment. As a specific example of a cleaned object covered with a resin mask, electronic components are examples of such objects. By performing at least one of the following processes—soldering with a resin mask and plating (copper plating, aluminum plating, nickel plating, tin plating, etc.)—wires or terminals are formed on the substrate surface. In this invention, soldering refers to the presence of solder on a portion of the substrate where the resin mask is absent, forming solder bumps by heating. In this invention, plating refers to performing at least one plating process selected from copper plating, aluminum plating, nickel plating, and tin plating on a portion of the substrate where the resin mask is absent. The absence of resin mask refers to the portion of the resin mask that has been removed during the development process in an resist pattern (a patterned resin mask) formed by developing a resin mask laminated onto a substrate. Therefore, this invention relates to the use of a cleaning agent composition of this invention as a cleaning agent in the manufacture of electronic components.

In one or more embodiments, the object to be cleaned undergoes at least one step of soldering and plating a substrate having an anti-corrosion pattern (a patterned resin mask) formed by developing a resin mask laminated onto a substrate. For example, the object to be cleaned may be a substrate having a portion where a resin mask with a hardened anti-corrosion layer is formed on the substrate, and a portion where solder bumps or a plating layer are formed in the portion where the resin mask is not formed.

The object to be cleaned, in one or more embodiments, is a substrate having a resin mask with micro-gaps. In this invention, the gap, in one or more embodiments, refers to the distance between patterns (the spacing between adjacent wirings), also called space (S). Furthermore, the width of the pattern (wiring) is also called line (L). The resin mask with micro-gaps, in one or more embodiments, refers to a resin mask with a spatial width of 10 μm or less. For example, a resin mask with a spatial width of 4–7 μm can be cited as an example of a resin mask with micro-gaps.

The cleaning agent composition of the present invention, in one or more embodiments, is effective in cleaning objects with a resin mask attached, or further coated and/or heat-treated resin mask, from the viewpoint of cleaning effect. The resin mask can be, for example, a negative resin mask or a positive resin mask. In the present invention, a negative resin mask refers to one formed using a negative resist agent, such as a negative resist layer that has undergone exposure and/or development. In this invention, a positive resin mask refers to one formed using a positive resist agent, such as a positive resist layer that has been exposed and/or developed.

[Cleaning Method] In one or more embodiments, the cleaning method of the present invention includes the following step (hereinafter also referred to as the "peeling step"): using the cleaning agent composition of the present invention, peeling the resin mask from a substrate (the object to be cleaned) having a copper-containing metal layer and a resin mask on its surface. In one or more embodiments, the peeling step includes bringing the object to be cleaned into contact with the cleaning agent composition of the present invention. In one or more embodiments, the peeling step includes removing the resin mask present in the micro-gap. The resin mask existing in the micro-gaps, as described above, is a resin mask existing in a space with a width of less than 10 μm. According to the cleaning method of this invention, the removability (peelability) of the resin mask is not significantly compromised, and the residue on the substrate after cleaning is not significantly increased, thus inhibiting copper corrosion.

Methods for using the detergent composition of the present invention to peel off the resin mask from the object to be cleaned, or methods for bringing the object to be cleaned into contact with the detergent composition of the present invention, include, for example, immersion in a cleaning bath containing the detergent composition, spraying the detergent composition into contact (spraying method), and ultrasonic cleaning by irradiating with ultrasound during immersion. The detergent composition of the present invention can be used directly for cleaning without dilution. Examples of objects to be cleaned include those described above.

The cleaning method of the present invention, in one or more embodiments, may include the steps of contacting the detergent composition with the object to be cleaned, rinsing with water, and then drying. The cleaning method of the present invention, in one or more embodiments, may include the step of contacting the detergent composition with the object to be cleaned, and then rinsing with water.

From the viewpoint of easily leveraging the cleaning power of the cleaning agent composition of the present invention, it is preferable to irradiate the cleaning agent composition of the present invention with ultrasound when it comes into contact with the object being cleaned, and more preferably, the ultrasound is of a higher frequency. From the same viewpoint, the irradiation conditions of the aforementioned ultrasound are, for example, preferably 26–72 kHz and 80–1500 W, more preferably 36–72 kHz and 80–1500 W.

In the cleaning method of the present invention, from the viewpoint of easily exerting the cleaning power of the cleaning agent composition of the present invention, the temperature of the cleaning agent composition is preferably above 40°C, more preferably above 50°C, and from the viewpoint of reducing the impact on the substrate, it is preferably below 70°C, more preferably below 60°C.

[Manufacturing Method of Electronic Components] This invention relates to a method for manufacturing an electronic component (hereinafter also referred to as "the manufacturing method of the electronic component of the invention"), which includes a step (cleaning step) of cleaning a substrate (the object to be cleaned) having a copper-containing metal layer and a resin mask on its surface using the cleaning method of the invention. Examples of the object to be cleaned include the aforementioned object. In one or more embodiments of the manufacturing method of the electronic component of the invention, at least one step of performing at least one of the following treatments—soldering and plating with a resin mask—on at least one type of electronic component selected from printed circuit boards, wafers, and metal plates prior to the aforementioned cleaning step may be included. In one or more embodiments, the manufacturing method of the electronic components of this invention may include an etching step of the copper-containing metal layer after the aforementioned cleaning step. By using the cleaning method of this invention, the manufacturing method of the electronic components of this invention can effectively prevent damage to the removability (peelability) of the resin mask and inhibit copper corrosion by not significantly increasing the residue on the substrate after cleaning. Therefore, it can manufacture electronic components with higher reliability. Furthermore, by using the cleaning method of this invention, the resin mask adhering to the electronic components can be easily removed, thus shortening the cleaning time and improving the manufacturing efficiency of the electronic components.

[Kit] This invention relates to a kit (hereinafter also referred to as "the kit of the invention") used in either the cleaning method of the invention or the manufacturing method of the electronic components of the invention. In one or more embodiments, the kit of the invention is a kit for manufacturing the cleaning agent composition of the invention. According to the kit of the invention, a cleaning agent composition that inhibits copper corrosion without significantly impairing the resin mask removal (peelability) and without significantly increasing the residue on the cleaned substrate can be obtained.

As one embodiment of the present invention, an example is a two-component detergent set comprising, in an immiscible state, a solution containing component A (component 1) and a solution containing component B (component 2). At least one of the first and second solutions further contains part or all of water (component C), and the first and second solutions are mixed upon use. After mixing, the first and second solutions can be diluted with water (component C) as needed. Each of the first and second solutions may also contain any of the aforementioned components as needed. Example

The present invention will now be described in detail with reference to embodiments, but the present invention is not limited by such embodiments.

1. Preparation of the detergent compositions of Examples 1-13, Comparative Example 1, and Reference Examples 1-2 The detergent compositions of Examples 1-13, Comparative Example 1, and Reference Examples 1-2 were prepared by mixing the components shown in Table 1 according to the mixing amounts (mass %, effective fraction) recorded in Table 1, followed by stirring and mixing.

The detergent compositions of Examples 1-13, Comparative Example 1, and Reference Examples 1-2 were prepared using the following components. (Ingredient A) TMAH: Tetramethylammonium hydroxide [Manufactured by Showa Denko Co., Ltd., concentration 25%] MEA: Monoethanolamine [Manufactured by Nippon Shokubai Co., Ltd.] (Ingredient B) Ascorbic acid [Fujifilm and Wako Junya Co., Ltd.] HOPO: 2-Hydropyridine-N-oxide [Manufactured by Suzhou Haofan Biotechnology Co., Ltd.] (Ingredient C) Water [Pure water with a concentration of less than 1 μS/cm produced by Organo Co., Ltd.'s G-10DSTSET water purification plant] (Ingredient D) BDG: Diethylene glycol monobutyl ether [Manufactured by Nippon Emulsifier Co., Ltd., diethylene glycol monobutyl ether] (Ingredient E) HEDP: Etidromic acid [Manufactured by Italmatch Japan Co., Ltd., Dequest 2010, concentration 60%] (Ingredient F) Ammonium formate [Manufactured by Toyama Pharmaceutical Co., Ltd.] (Other ingredients) Benzotriazole [Mitsui Fine Chemicals Co., Ltd.] (Coated etching inhibitor) Thioacetamide [Fuji Film & Koujun Pharmaceutical Co., Ltd.] (Coated etching inhibitor)

2. Evaluation of Detergent Compositions The detergent compositions prepared in Examples 1-13, Comparative Example 1, and Reference Examples 1-2 were evaluated as follows.

[Preparation of Test Piece I] A photosensitive film for forming a PKG (Semiconductor Packaging) substrate circuit was laminated onto the surface of the substrate after electroless plating under the following conditions. Selective exposure treatment was performed to harden the exposed areas (exposure step). Then, unexposed areas were removed by development treatment (development step), resulting in a substrate with an anti-corrosion pattern (a negative resin mask with a pattern shape). Furthermore, copper plating (10 μm thickness) was performed on the areas where unexposed areas were removed using the aforementioned development treatment, thereby obtaining Test Piece I (50 mm × 50 mm) of a substrate comprising a copper-containing metal layer (copper wiring) and a hardened anti-corrosion layer, i.e., a resin mask. (1) Lamination: Using a cleaning roller (RAYON INDUSTRIAL, Inc., RY-505Z) and a vacuum coater (Rohm and Haas, VA7024/HP5), lamination was performed at a roller temperature of 50°C and a roller pressure of 1.4 Bar. (2) Exposure: Using a direct-drawing device for printed circuit boards (SCREEN Graphic and Precision Solutions, Inc., Mercurex LI-9500), exposure was performed at an exposure dose of 15 mJ/ ^cm² . (3) Pattern shape: L/S = 5 μm/5 μm, 6 μm/6 μm, 7 μm/7 μm stripe patterns. Furthermore, L/S represents: the line (L) representing the width of the pattern (copper wiring) and the space (S) representing the distance between adjacent patterns (width of the insulation). (4) Development: Using a substrate development apparatus (manufactured by Yangbo Technology Co., Ltd., LT-980366) and a 1% sodium carbonate aqueous solution at 30°C, the resin mask of the unexposed area is removed under a spray pressure of 0.2 MPa.

[Cleaning Test] Use the various detergent compositions to clean test piece I, and peel off the resin mask from the substrate. Add 3 kg of the detergent composition to a 5 L stainless steel beaker, heat to 50°C, and circulate the solution in a box-type spray cleaner equipped with a single-fluid nozzle (density tapered) J020 (manufactured by H.IKEUCHI Co., Ltd.) as the spray nozzle while spraying test piece I (pressure: 0.1 MPa, spray distance: 8 cm) for 1 minute (peeling or cleaning step). Then, rinse in a 1 L glass beaker containing 1 kg of water, and dry with nitrogen.

[Evaluation of Resin Mask Peelability I] Using a VHX-6000 digital optical microscope (manufactured by Keyence Corporation), the pattern area of sample I after the above-mentioned cleaning test was visually confirmed at 500x magnification to check for any residual resin mask. The following criteria were used for evaluation. The results are shown in Table 1. <Evaluation Criteria> A: No residue found at 5 μm/5 μm B: No residue found up to 6 μm/6 μm C: No residue found up to 7 μm/7 μm D: Residue still found at 7 μm/7 μm

[Evaluation of Cu Etching Rate (Evaluation of Copper Corrosion)] The detergent mixture was adjusted to 2.5 L, heated to 50°C, and sprayed (pressure: 0.05 MPa, spray distance: 80 mm) for 4 minutes on a test piece I with copper plating (25 ^cm² per side, 50 ^cm² on both sides) in a box-type spray cleaner equipped with a dense tapered nozzle (manufactured by H.IKEUCHI Co., Ltd., J020) as the spray nozzle. After diluting the detergent mixture, the amount of copper leached was determined using ICP (Inductively Coupled Plasma) analysis (manufactured by Agilent Technologies, Agilent 5110 ICP-OES). The copper density was set to 8.94 g/ ^cm³ , and the Cu etching rate (μm/min) was evaluated based on the amount of leached copper. The results are shown in Table 1. A lower Cu etching rate indicates better copper corrosion inhibition. Cu etching rate (μm/min) = Amount of copper leached (by weight) ÷ Copper density ÷ Coating area ÷ Processing time

[Residual Components] The copper-plated portion of the substrate samples that underwent the above cleaning test was analyzed using X-ray photoelectron spectroscopy. Based on the signal intensity of carbon, oxygen, nitrogen, and sulfur atoms, the residual properties were evaluated according to the following criteria. The results are shown in Table 1. If significant signals from carbon, oxygen, nitrogen, and sulfur atoms are detected, it is determined that components from the detergent composition remain on the cleaned substrate. <Evaluation Criteria> A: No signal detected, or only a weak signal detected B: Significant signal detected

[Stability] Visually observe the changes in the color or turbidity of the detergent composition before and after the above cleaning test, and evaluate them according to the following criteria. The results are shown in Table 1. <Evaluation Criteria> A: No change observed before and after the cleaning test B: Change observed before and after the cleaning test

[Table 1] Table 1 Comparative example Implementation Examples Reference 1 1 2 3 4 5 6 7 8 9 10 11 12 13 1 2 Mixing quantity (mass %) Ingredient A TMAH 4.0 4.0 4.0 4.0 1.0 7.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 MEA 6.0 6.0 2.0 8.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 Component B Ascorbic acid 0.5 0.5 0.5 0.5 0.5 0.2 1.0 0.5 HOPO 0.5 0.5 0.5 0.5 0.5 Ingredient C water 90.0 89.5 93.5 87.5 92.5 86.5 89.8 89.0 89.5 86.5 87.7 89.0 84.2 84.2 84.2 84.2 Ingredient D BDG 3.0 3.0 3.0 3.0 3.0 Ingredient E HEDP 1.8 1.8 1.8 1.8 1.8 Ingredient F ammonium formate 0.5 0.5 0.5 0.5 0.5 Other ingredients benzotriazole 0.5 Thioacetamide 0.5 Total (%) 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Mass ratio A/B - 20 12 twenty four 14 26 50 10 20 20 20 20 20 20 - - Peelability I B B C B B B B B B B B B A A B B Corrosivity: Cu etching rate (µm/min) 0.05 0.02 0.02 0.03 0.03 0.02 0.03 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.00 Residual properties of ingredients A A A A A A A A A A A A A A B B Stability of detergent composition A B B B B B B B A A A A A B A A

As shown in Table 1, it can be seen that the detergent compositions of Examples 1 to 13, compared with Comparative Example 1 and Reference Examples 1 to 2 which do not contain component B, can inhibit copper corrosion without significantly impairing the removal of resin masking and without significantly increasing the residue on the substrate after cleaning.

The detergent compositions of Example 1 and Comparative Example 1 were then evaluated as follows.

[Test Piece II] A photosensitive film for forming a PKG (semiconductor packaging) substrate circuit was laminated onto the surface of the substrate after electroless plating under the following conditions. Selective exposure processing was performed to harden the exposed areas (exposure step). Unexposed areas were then removed by development processing (development step), resulting in a substrate with an anti-corrosion pattern (a negative resin mask with a pattern shape). Furthermore, copper plating (50 μm thickness) was performed on the areas where unexposed areas were removed using the aforementioned development processing, thereby obtaining Test Piece II (50 mm × 50 mm) of a substrate comprising a copper-containing metal layer (copper wiring) and a hardened anti-corrosion layer, i.e., a resin mask. (1) Lamination: Using a cleaning roller (RAYON INDUSTRIAL, Inc., RY-505Z) and a vacuum coater (Rohm and Haas, VA7024/HP5), lamination was performed at a roller temperature of 50°C and a roller pressure of 1.4 Bar. (2) Exposure: Using a direct-drawing device for printed circuit boards (SCREEN Graphic and Precision Solutions, Inc., Mercurex LI-9500), exposure was performed at an exposure dose of 15 mJ/ ^cm² . (3) Pattern shape: A strip pattern with L/S = 20 μm/20 μm. Furthermore, L/S represents: the line (L) representing the width of the pattern (copper wiring) and the space (S) representing the distance between adjacent patterns (width of the insulation). (4) Development: Using a substrate development device (manufactured by Yangbo Technology Co., Ltd., LT-980366) and a 1% sodium carbonate aqueous solution at 30°C, the resin mask of the unexposed area is removed under a spray pressure of 0.2 MPa.

[Cleaning Test] Use the various detergent compositions to clean test piece II, and peel off the resin mask from the substrate. Add 3 kg of the detergent composition to a 5 L stainless steel beaker, heat to 50°C, and circulate the solution in a box-type spray cleaner equipped with a single-fluid nozzle (density tapered) J020 (manufactured by H.IKEUCHI Co., Ltd.) as the spray nozzle while spraying test piece II (pressure: 0.1 MPa, spray distance: 8 cm) for 10 minutes (peeling or cleaning step). Then, rinse the fish in a 1 L glass beaker filled with 1 kg of water, and dry it with nitrogen.

[Evaluation of Resin Mask Peelability II] Using a VHX-6000 digital optical microscope (manufactured by Keyence Corporation), the pattern area of the sample II after the above cleaning test was visually confirmed at 500x magnification to check for any residual resin mask. The following criteria were used for evaluation. The results are shown in Table 2. <Evaluation Criteria> A: 2 or fewer residues per wafer B: 3 to 9 residues per wafer C: 10 to 20 residues per wafer D: 21 or more residues per wafer

[Evaluation of Cu Etching Rate (Evaluation of Copper Corrosion)] The evaluation of copper corrosion in specimen II was performed in the same manner as that in specimen I. The results are shown in Table 2.

[Table 2] Table 2 Comparative example Implementation Examples 1 1 Mixing quantity (mass %) Ingredient A TMAH 4.0 4.0 MEA 6.0 6.0 Component B Ascorbic acid 0.5 Ingredient C water 90.0 89.5 Total (quality%) 100.0 100.0 Mass ratio A/B - 20 Dissociative II C A Corrosivity: Cu etching rate (µm/min) 0.05 0.02

As shown in Table 2, the detergent composition of Example 1, compared to Comparative Example 1 which does not contain component B, demonstrates improved resin mask removal and inhibits copper corrosion. [Industrial Applicability]

According to the present invention, a cleaning method is provided that can inhibit copper corrosion without significantly impairing the removability (peelability) of the resin mask and without significantly increasing the residue on the substrate after cleaning. The cleaning method of the present invention can shorten the cleaning steps of electronic components with resin masks and improve the performance and reliability of the manufactured electronic components, thereby improving the manufacturability of semiconductor devices.

Claims (14)

A method for cleaning a substrate includes the following steps: using a cleaning agent composition containing component A, component B, and component C, peeling off a resin mask from a substrate having a copper-containing metal layer and a resin mask on its surface; the content of component A is 5% to 15% by mass, and the content of component B is 0.05% to 5% by mass; component A: quaternary ammonium hydroxide represented by formula (I) and amine represented by formula (II); component B: reducing agent; component C: water [Chemical 1] In formula (I) above, ^R1 , ^R2 , ^R3 and ^R4 are each independently selected from at least one of methyl, ethyl, propyl, hydroxymethyl, hydroxyethyl and hydroxypropyl; [Chemical 2] In formula (II) above, ^R5 represents at least one of hydrogen atom, methyl, ethyl and aminoethyl, ^R6 represents at least one of hydrogen atom, hydroxyethyl, hydroxypropyl, methyl and ethyl, and ^R7 represents at least one of aminoethyl, hydroxyethyl and hydroxypropyl. The cleaning method described in Request 1, wherein the copper metal layer is a copper plating layer. For example, in the cleaning method of claim 1, the resin mask is a hardened anti-corrosion layer. As in the cleaning method of claim 1, component B is selected from one or more N-oxide compounds containing a nitrogen-containing heteroaromatic ring in which at least one hydrogen atom of the ring is replaced by a hydroxyl group. The cleaning method of claim 1, wherein the substrate has a copper-containing metal layer with a thickness of 15 μm or more. The cleaning method of claim 1, wherein the step of peeling off the resin mask includes removing the resin mask present in the micro-gaps. The cleaning method of any one of claims 1 to 6, wherein the substrate having a copper metal layer and a resin mask on its surface has undergone at least one of the following steps: soldering and plating with a resin mask. A method for manufacturing an electronic component includes the following steps: cleaning a substrate having a copper-containing metal layer and a resin mask on its surface using a cleaning method as described in any of claims 1 to 7. A detergent composition for removing resin masks, comprising the following components A, B, and C; the content of component A is 5% to 15% by mass, and the content of component B is 0.05% to 5% by mass; Component A: a quaternary ammonium hydroxide represented by formula (I) and an amine represented by formula (II); Component B: a reducing agent; Component C: water. In formula (I) above, ^R1 , ^R2 , ^R3 and ^R4 are each independently selected from at least one of methyl, ethyl, propyl, hydroxymethyl, hydroxyethyl and hydroxypropyl; [Chemical 4] In formula (II) above, ^R5 represents at least one of hydrogen atom, methyl, ethyl and aminoethyl, ^R6 represents at least one of hydrogen atom, hydroxyethyl, hydroxypropyl, methyl and ethyl, and ^R7 represents at least one of aminoethyl, hydroxyethyl and hydroxypropyl. As in claim 9, the detergent composition wherein component B is at least one of ascorbic acid and 2-hydroxypyridine-N-oxide. For example, in the detergent composition of Request 9, the total amount of component A, component B and component C is 90% by mass or more. For example, in the detergent composition of claim 9, the content of component C is 60% by mass or more. The cleaning agent composition for removing resin mask as described in any of claims 9 to 12, wherein the resin mask is a mask for copper or tin plating. The purpose of a cleaning agent composition for resin masking removal is as a cleaning agent in the manufacture of electronic components. The cleaning agent composition for resin masking removal contains the following components A, B, and C; the content of component A is 5% to 15% by mass, and the content of component B is 0.05% to 5% by mass; Component A: a quaternary ammonium hydroxide represented by formula (I) and an amine represented by formula (II); Component B: a reducing agent; Component C: water. In formula (I) above, ^R1 , ^R2 , ^R3 and ^R4 are each independently selected from at least one of methyl, ethyl, propyl, hydroxymethyl, hydroxyethyl and hydroxypropyl; [Chemical 6] In formula (II) above, ^R5 represents at least one of hydrogen atom, methyl, ethyl and aminoethyl, ^R6 represents at least one of hydrogen atom, hydroxyethyl, hydroxypropyl, methyl and ethyl, and ^R7 represents at least one of aminoethyl, hydroxyethyl and hydroxypropyl.